JP2006303398A - Hole-filled multilayered printed wiring board and manufacturing method thereof, and two-stage curing type resin composition used for manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce a polishing cost and shorten a manufacturing process to prevent a substrate from being deformed (changes in the dimensions) with polishing, by omitting the polishing process of a hole-filled surface in the manufacturing method of the hole-filled multilayered printed wiring board. <P>SOLUTION: In the manufacturing method of the hole-filled multilayered printed wiring board, a two-stage curing type resin composition is filled in the through-holes of a both-sided printed wiring board; a first stage curing of the filled resin is performed by heating the board at 100-200°C or irradiation; and a conductive pattern is formed from the copper foil of a surface layer, after the both-sided printed wiring board has been sandwiched between (a) a copper foil with resin and the copper foil with the resin or (b) the copper foil with the resin and a prepreg is lamination-pressed by heating. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hole-filled multilayer printed wiring board and a method for producing the same, and a two-stage curable resin composition used exclusively for the method for producing the same.

  The inventors of the present application previously disclosed a light / heat two-stage curable resin composition suitable as a material for filling a through hole in a multilayer printed wiring board, a multilayer printed wiring board filled with this resin, a method for manufacturing the same, and the like. (Patent Document 1).

  The above-mentioned hole-filled multilayer printed wiring board is excellent in that the cured resin portion filled in the hole is not dented, cracks or the like are generated, the solder resistance is excellent, and the metal portion is not corroded. By using such a hole-filled multilayer printed wiring board, it is possible to manufacture a highly reliable and long-life electric product that does not cause a short circuit or poor electrical connection.

  The hole-filled multilayer printed wiring board is, for example, filled with a two-stage curable resin composition in a through-hole of a double-sided copper-clad laminate, and subjected to the first-stage curing of the filled resin by UV irradiation, and the double-sided copper-clad laminate surface The two-sided copper foil is made into a conductor pattern, the surface of the resin-coated copper foil is coated, and the second stage thermosetting of the first-stage cured resin is performed by laminating and pressing under heating. It can manufacture by heat-curing and forming a conductor pattern from the copper foil of copper foil with resin after that.

JP2003-105061A.

  The inventors of the present application further develop the method for manufacturing a hole-filled multilayer printed wiring board described in Patent Document 1 above, and an object thereof is to omit the polishing step without impairing the advantages of the invention.

  As a result, the polishing cost can be reduced and the manufacturing process can be shortened. Furthermore, deformation (dimensional change) of the substrate due to polishing can be avoided.

In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, have reached the following present invention.
That is, the present invention fills a through-hole of a double-sided printed wiring board with a two-stage curable resin composition, and performs the first-stage curing of the filled resin by heating at 100 to 200 ° C. or UV irradiation. A) Copper foil with resin and copper foil with resin, or b) Lamination between the copper foil with resin and the prepreg, laminating and pressing at the second stage curing temperature or higher, and then the conductor pattern from the copper foil on the surface layer A method for manufacturing a hole-filled multilayer printed wiring board to be formed is provided.

  Preferably, in the present invention, the two-stage curable resin composition includes the following components [I], [II], [III], [V], and [VI]. Provided is a method for producing the above-described hole-filled multilayer printed wiring board, which is a photo-thermosetting resin composition B containing A or the following components [I], [II], [IV], [V], and [VI]. To do.

[I]: Unsaturated fatty acid partial adduct of epoxy resin.
[II]: (Meth) acrylates.
[III]: radical thermal polymerization initiator.
[IV]: Photocrosslinking agent.
[V]: Epoxy resin.
“VI”: latent curing agent.

  More preferably, this invention provides the manufacturing method of the said hole-filling multilayer printed wiring board whose said component [V]: epoxy resin is a crystalline epoxy resin and / or a liquid epoxy resin.

  Furthermore, the present invention provides a hole-filled multilayer printed wiring board manufactured by any one of the above manufacturing methods.

  Further, according to the present invention, the two-stage curable resin composition is the thermo / thermosetting resin composition A or the photo / thermosetting resin composition B, and the manufacturing of the hole-filled multilayer printed wiring board of the present invention is exclusively performed. Provided is a two-stage curable resin composition used only in the method.

  Preferably, in the present invention, the component [V] in the thermo / thermosetting resin composition A or the photo / thermosetting resin composition B: the epoxy resin is a crystalline epoxy resin and / or a liquid epoxy resin. A two-stage curable resin composition is provided.

  The thermo / thermosetting resin composition A or the photo / thermosetting resin composition B can be used in addition to the method for producing a hole-filled multilayer printed wiring board according to the present invention. Only what is used for the manufacturing method of the hole-filling multilayer printed wiring board of this invention is claimed.

  Since the polishing process can be omitted by the method for manufacturing a hole-filled printed wiring board of the present invention, the polishing cost is reduced and the manufacturing process is shortened. Therefore, the hole-filled multilayer printed wiring board can be provided at a very low cost.

  Furthermore, by not performing polishing, it is possible to prevent deformation (dimensional change) of the substrate due to polishing. Therefore, it is possible to provide a hole-filled multilayer printed wiring board with extremely excellent dimensional accuracy.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
In the method for manufacturing a hole-filled multilayer printed wiring board according to the present invention, first, the through-holes of the double-sided printed wiring board are filled with a two-stage curable resin composition to fill the through-holes.

  In the production method of the present invention, examples of the double-sided printed wiring board include a rigid printed wiring board, a flexible printed wiring board, and a rigid flex printed wiring board.

  A hole-filled multilayer printed wiring board can be manufactured by using a conductor pattern-unformed (double-sided copper-clad laminate etc.) instead of the double-sided printed wiring board. However, a conductor pattern already formed is preferable for the following reasons. That is, when a conductor pattern-unformed one is used, it is necessary to form a conductor pattern in a subsequent process (for example, before a thermosetting adhesive sheet coating process described later). However, if a defect occurs in this conductor pattern forming process, the substrate in the process of production must be discarded, and there is a possibility that all of the previous manufacturing processes will be wasted.

  Examples of the through hole include all kinds of holes penetrating through the printed wiring board. Specifically, examples of the through hole include a through via hole, a component hole, and other through holes.

  Examples of the two-stage curable resin composition include a thermo / thermosetting resin composition in which both first-stage curing and second-stage curing are performed by heating. Preferably, the thermo / thermosetting resin composition includes the following components [I], [II], [III], [V], and [VI] (hereinafter referred to as “thermo / thermosetting resin composition”). And may be referred to as “product A”.).

[I]: Unsaturated fatty acid partial adduct of epoxy resin.
[II]: (Meth) acrylates.
[III]: radical thermal polymerization initiator.
[V]: Epoxy resin.
[VI]: Latent curing agent.

  Preferably, specific examples of the thermo-thermosetting resin composition A include those described in JP-A No. 2003-26765.

  The thermosetting resin composition A contains, as component [I], an unsaturated fatty acid partial adduct of an epoxy resin. The epoxy value of the epoxy resin that is the raw material for preparing the component [I] (hereinafter sometimes simply referred to as “raw material epoxy resin”) is, for example, preferably 130 to 400, particularly 150 to 250. Examples of the epoxy resin for raw materials include phenol novolac type epoxy resins, epoxy resins from polyfunctional phenols, naphthalene skeleton epoxy resins, glycidyl amine epoxy resins, triazine skeleton epoxy resins, glycidyl ester epoxy resins, and alicyclic types. An epoxy resin etc. are mentioned.

  Preferably, as the raw material epoxy resin, each compound represented by the formulas [Chemical I-E1] to [Chemical I-E7] shown in Table 1, particularly phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenyl A methane type epoxy resin, a bisphenol A novolak type epoxy resin, a dicyclopentadiene phenol type epoxy resin, etc. are mentioned, and one or more of these may be used.

  Throughout this application document, where G is a glycidyl group, i.e. the following formula, unless clearly used otherwise:

を表す。

Represents.

In the formulas [Chemical I-E1] to [Chemical I-E3], n represents an integer of 0 to 30. In the formulas [Chemical I-E4] to [Chemical I-E6], n represents an integer of 1 to 30. In the formula [Chemical I-E7], n represents an integer of 2 to 50. In the formula [Chemical I-E2], R ¹ and R ² each independently represent H or CH ₃ .

  As an unsaturated fatty acid which is the other preparation raw material of component [I], for example, the following formula [Chemical Formula I-UFA],

［式中、Ｒ^１〜Ｒ^３は、それぞれ独立に、Ｈ又はＣＨ_３を表す。］
で表されるものが挙げられる。具体的には不飽和脂肪酸としては、アクリル酸、メタクリル酸、クロトン酸等が挙げられる。

[Wherein, R ^{1 to} R ³ each independently represent H or CH ₃ . ]
The thing represented by is mentioned. Specific examples of the unsaturated fatty acid include acrylic acid, methacrylic acid, and crotonic acid.

  Component [I] may be prepared by a conventional preparation method. For example, one or more types of raw material epoxy resins and one or more types of unsaturated fatty acids [for example, acrylic acid and / or methacrylic acid (hereinafter sometimes simply referred to as “(meth) acrylic acid”)] are used as necessary. It may be prepared by stirring and mixing under heating.

  Component [I] is a product obtained by partially adding an unsaturated fatty acid to an epoxy resin. That is, in the unsaturated fatty acid partial adduct of the epoxy resin, at least one epoxy group remains in the epoxy resin after the addition of the unsaturated fatty acid. Specifically, the unsaturated fatty acid is preferably added to 20 to 80%, particularly 40 to 60% of the epoxy group in the raw material epoxy resin. Those having an unsaturated fatty acid addition amount of less than 20% (simply referred to as “less than 20% unsaturated fatty acid adduct”, the same shall apply hereinafter) have adhesiveness to the thermosetting resin composition. In some cases, the excess resin cannot be removed well when applied to the substrate. On the other hand, an 80% excess unsaturated fatty acid adduct may cause the first-stage cured film to become hard, and the flatness of the surface after the laminating press described later may be impaired.

  Examples of component [I] include adducts of novolac type epoxy resin and (meth) acrylic acid (specifically, adducts of cresol novolac type epoxy resin and acrylic acid, etc.). The above may be contained in the thermosetting / thermosetting resin composition A.

  Preferably, as the component [I], an acrylic acid partial adduct of a phenol novolac type epoxy resin, an acrylic acid partial adduct of a cresol novolac type epoxy resin, an acrylic acid partial adduct of a trisphenylmethane type epoxy resin, or a bisphenol A novolak Methacrylic acid partial adduct of type epoxy resin, methacrylic acid partial adduct of dicyclopentadiene phenol type epoxy resin, crotonic acid partial adduct of phenol novolac type epoxy resin and the like, and one or more of these may be used.

  The thermo / thermosetting resin composition A contains (meth) acrylates (that is, acrylates and / or methacrylates) as component [II]. In the component [II], examples of the acrylate include esterified products of acrylic acid and a hydroxy compound. Examples of the methacrylates include esterified products of methacrylic acids and hydroxy compounds.

  Examples of the acrylic acids and methacrylic acids include unsaturated fatty acids represented by the above formula [Chemical I-UFA]. Specific examples of acrylic acids and methacrylic acids include acrylic acid, methacrylic acid, and crotonic acid.

  Examples of the hydroxy compound include alcohols, (hemi) acetals or (hemi) ketals, and hydroxy acid esters. Examples of alcohols include lower alcohols, ring alcohols, polyhydric alcohols, and aromatic alcohols. In the hydroxy compound, examples of (hemi) acetal or (hemi) ketal include condensates of the above alcohols (for example, ring alcohols, polyhydric alcohols, etc.) with formaldehyde and hydroxyaldehyde. In the hydroxy compound, specific examples of the hydroxy acid ester include caprolactone ring-opening adduct of furfuryl alcohol, neopentyl glycol hydroxypivalate, and the like.

  Component [II] preferably has a single cured product having a Tg (° C.) of 80 to 180, particularly 120 to 150. If the Tg is less than 80, the first-stage cured film may become sticky. Conversely, if it exceeds 180, the first stage cured film may become too hard.

  Preferably, as the component [II], each compound represented by the formulas [Chemical Formula II-1] to [Chemical Formula II-9] shown in Table 2, particularly isobornyl acrylate, dicyclopentanyl methacrylate, hydroxybivalin. Examples include acid neopentyl glycol diacrylate, tricyclodecane dimethanol acrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, isobornyl crotonic acid, and the like, and one or more of these may be contained.

  The thermo-thermosetting resin composition A contains a radical thermopolymerization initiator related to the first stage curing reaction as component [III]. As the component [III], for example, a radical thermal polymerization initiation temperature of 60 to 150 ° C., particularly 90 to 120 ° C. is preferable. Furthermore, the component [III] is preferably one in which an unsaturated bond (particularly, derived from the unsaturated fatty acid) is involved in the first-stage curing reaction instead of an epoxy group.

  Specific examples of such component [III] include t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanate, dicumyl peroxide, and the like. Good.

  The thermosetting / thermosetting resin composition A contains an epoxy resin as component [V]. Examples of the epoxy resin include a crystalline epoxy resin and / or a liquid epoxy resin. In the component [V], as the crystalline epoxy resin, those having a melting point higher than normal temperature and lower than the first stage curing reaction start temperature, for example, 80 to 110 ° C., particularly 90 to 105 ° C. are preferable. Furthermore, as a crystalline epoxy resin, the viscosity (mPa · s) is preferably 50 or less, particularly 0.1 to 20 at the melting point to the first stage curing reaction start temperature. Further, as the crystalline epoxy resin, those hardly soluble in the thermo-thermosetting resin composition A are preferable.

  Examples of the crystalline epoxy resin include crystalline epoxy resins such as biphenyl type, diphenyl type, hydroquinone type, biphenyl novolac type, and fluorin type, and one or more of these may be contained.

  Examples of the biphenyl type crystalline epoxy resin include the following formula [Chemical Vc-1],

［式中、ＲはＨ若しくはＣＨ_３を表す。］
で表されるものが挙げられ、これらの一種以上含有してよい。

[Wherein R represents H or CH ₃ . ]
These may be included, and one or more of these may be contained.

  As the diphenyl type crystalline epoxy resin, for example, the following formula [Chemical Vc-2],

［式中、ＸはＯ若しくはＳを表し、並びにＲ^１及びＲ^２は、それぞれ独立に、Ｈ、ＣＨ_３若しくはｔ−ブチルを表す。］
で表されるものが挙げられ、これらの一種以上含有してよい。

[Wherein, X represents O or S, and R ¹ and R ² each independently represent H, CH ₃ or t-butyl. ]
These may be included, and one or more of these may be contained.

  As hydroquinone type crystalline epoxy resin, for example, the following formula [Chemical Vc-3],

［式中、ｎは０、１若しくは２を表す。］
で表されるものが挙げられ、これらの一種以上含有してよい。

[Wherein n represents 0, 1 or 2. ]
These may be included, and one or more of these may be contained.

  Examples of the biphenyl novolac type crystalline epoxy resin include the following formula [Vc-4],

［式中、ｎは１若しくは２を表す。］
で表されるものが挙げられ、これらの一種以上含有してよい。

[Wherein n represents 1 or 2. ]
These may be included, and one or more of these may be contained.

  As the fluorescein type crystalline epoxy resin, for example, the following formula [Chemical Vc-5],

で表されるものが挙げられる。

The thing represented by is mentioned.

  Preferably, examples of the crystalline epoxy resin include tetramethylbiphenyl type epoxy resin, hydroquinone diglycidyl ether, di- (p-glycidylphenyl) ether, and the like.

  In component [V], the liquid epoxy resin refers to an epoxy resin that is in a liquid or semi-solid state at room temperature, and examples thereof include an epoxy resin that has fluidity at room temperature. As such a liquid epoxy resin, for example, the viscosity (room temperature, mPa · s) is 20000 or less, particularly preferably 1000 to 10,000.

  Specifically, as the liquid epoxy resin, the following formula [Formula Vl-1],

［式中、ｎは０若しくは１を表す。］
で表されるビスフェノールＡ型エポキシ樹脂が挙げられ、これらの一種以上含有してよい。

[Wherein n represents 0 or 1; ]
The bisphenol A type epoxy resin represented by these is mentioned, You may contain these 1 or more types.

  Furthermore, as a specific example of the liquid epoxy resin, the following formula [Chemical Vl-2],

［式中、ｎは０若しくは１を表す。］
で表されるビスフェノールＦ型エポキシ樹脂が挙げられ、これらの一種以上含有してよい。

[Wherein n represents 0 or 1; ]
The bisphenol F type epoxy resin represented by these is mentioned, You may contain these 1 or more types.

  Further, specific examples of the liquid epoxy resin include naphthalene type, diphenylthioether (sulfide) type, trityl type, alicyclic type, those prepared from the following alcohols, diallylbis A type , Methylresorcinol type, bisphenol AD type, N, N, O-tris (glycidyl) -p-aminophenol and the like, and one or more of these may be contained.

  Preferably, the liquid epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, N, N, O-tris (glycidyl) -p-aminophenol, bisphenol AD type epoxy resin, etc. You may contain more than a seed.

  The thermosetting / thermosetting resin composition A contains a latent curing agent as component [VI]. Component [VI] causes a second-stage curing reaction by heating. Examples of component [VI] include those having a second-stage curing reaction start temperature of 150 to 300 ° C, particularly 150 to 200 ° C.

Specifically, as component [VI], dicyandiamide (DICY), imidazole, BF ₃ -amine complex, amine adduct type curing agent, amine-acid anhydride (polyamide) adduct type curing agent, hydrazide type curing agent And carboxylic acid salts and onium salts of amine-based curing agents, and one or more of these may be contained.

  Specifically, in the component [VI], as the amine adduct type curing agent, an imidazole-based curing agent [2-ethyl-4-methylimidazole, 2-methylimidazole, 2,4-diamino-6- (2′- Methylimidazolyl- (1H))-ethyl-S-triazine and the like] or an adduct of an amine-based curing agent (such as diethylamine) and an epoxy compound, urea or an isocyanate compound. Examples of the hydrazide curing agent include adipic acid dihydrazide (ADH), sebacic acid dihydrazide (SDH), and the like. Examples of carboxylates of amine curing agents include nylon salts and ATU (3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane) / adipic acid Examples include salts. Examples of onium salts include sulfonium salts, ammonium salts, and phosphonium salts.

  Preferably, examples of the component [VI] include compounds represented by the formulas [Chemical VI-1] to [Chemical VI-3] shown in Table 3, and may contain one or more of these compounds.

  Various additives may be added to the thermosetting / thermosetting resin composition A as necessary. Examples of the additive include a filler, an organic / inorganic colorant, a flame retardant, an antifoaming agent, and the like.

  In the composition of the thermosetting resin composition A, the component [I] is 100 parts by weight, the component [II] is 50 to 300 parts by weight (particularly 150 to 250 parts by weight), and the component [III] is 5 to 5 parts by weight. 20 parts by weight (particularly 8-15 parts by weight), component [V] is 50-200 parts by weight (particularly 60-120 parts by weight), and component [VI] is 5-30 parts by weight (particularly 10-20 parts by weight). preferable.

  Preparation of thermosetting / thermosetting resin composition A is performed by, for example, mixing each component [I], [II], [III], [V], and [VI] and additives as necessary, and uniformly dispersing them. After that, vacuum degassing may be performed. The order of addition of each blending component is not particularly limited, and each blending component may be added sequentially or all blending components may be added at once.

  The thermo-thermosetting resin composition A prepared as described above preferably has a resin viscosity (Pa · S, room temperature) of 10 to 50, particularly 15 to 30.

  Furthermore, the two-stage curable resin composition of the present invention includes a photo / thermosetting resin composition in which the first stage curing is performed by light irradiation and the second stage curing is performed by heating. Preferably, as the photo / thermosetting resin composition, the components [I], [II], [V] and [VI], and the component [IV]: those containing a photocrosslinking agent (hereinafter referred to as “light • And may be referred to as “thermosetting resin composition B”).

  Preferably, specific examples of the photo / thermosetting resin composition B include those described in Patent Document 1 and JP-A No. 2004-75967.

  In the photo / thermosetting resin composition B, the components [I], [II], [V], and [VI] include those exemplified and explained in the thermo / thermosetting resin composition A. . In the photo / thermosetting resin composition B, the component [VI] preferably has, for example, a second-stage curing reaction start temperature of 150 to 300 ° C, particularly 150 to 200 ° C.

  The photo / thermosetting resin composition B contains a photocrosslinking agent as component [IV]. Examples of component [IV] include those that initiate a primary curing reaction by irradiation with light, for example, ultraviolet rays having a wavelength of 200 to 400 nm.

  Specifically, as component [IV], hydroxy ketones, benzyl methyl ketals, acyl phosphine oxides, amino ketones, benzoin ethers, benzoyl compounds, thioxanthones, biimidazoles, dimethylaminobenzoic acid esters , Sulfonium salts, anthraquinones, acridones, acridines, carbazoles, titanium complexes, and one or more of these.

  Preferably, examples of component [IV] include compounds represented by the formulas [Formula IV-1] and [Formula IV-2] shown in Table 4, and one or more of these may be contained.

  Various additives may be added to the light / thermosetting resin composition B as necessary. Examples of the additive include a filler, an organic / inorganic colorant, a flame retardant, an antifoaming agent, and the like. Specifically, examples of the additive include those described and exemplified as the “additive” in the thermosetting / thermosetting resin composition A.

  In the composition of the light / thermosetting resin composition B, the component [II] is 100 to 300 parts by weight (particularly 150 to 250 parts by weight) and the component [IV] is 1 to 50 parts per 100 parts by weight of the component [I]. Parts by weight (particularly 5 to 15 parts by weight), component [V] is 50 to 200 parts by weight (particularly 60 to 120 parts by weight), component [VI] is 1 to 50 parts by weight (particularly 5 to 20 parts by weight), and filling The agent is preferably 200 to 500 parts by weight (particularly 250 to 350 parts by weight).

  The photo / thermosetting resin composition B may be prepared in the same manner as the thermo / thermosetting resin composition A, for example.

  The light / thermosetting resin composition B prepared as described above preferably has a resin viscosity (Pa · S, room temperature) of 10 to 50, particularly 15 to 30 in view of applicability to the substrate.

  In the method for producing a hole-filled multilayer printed wiring board of the present invention, the through hole is filled by filling the through hole of the double-sided printed wiring board with the two-stage curable resin composition. The filling and filling of the through holes may be performed by, for example, screen printing (mask printing using a polyester screen or stainless steel screen), metal mask printing, roll coat printing, or the like.

In the method for manufacturing a hole-filled multilayer printed wiring board of the present invention, after filling and filling the through holes, the first-stage curing of the filled two-stage curable resin composition (filled resin) is performed. As the first stage curing conditions, for example, when the filling resin is the thermo-thermosetting resin composition A, the radical thermal polymerization start temperature of the component [III], specifically 100 to 200 (particularly 100 to 150). It can carry out by heating at 10 degreeC for 10 to 120 minutes. When the filling resin is the light / thermosetting resin composition B, light in the characteristic absorption wavelength region of the component [IV], specifically, ultraviolet light having a wavelength of 200 to 400 nm is 0.5 to 10 J / cm ² . Irradiation can be performed at −20 to 80 ° C. with a light irradiation amount. The photocuring may be performed using an in-liquid exposure apparatus described in JP-A-9-6010 and JP-A-10-29247.

  In one aspect of the method for producing a hole-filled multilayer printed wiring board according to the present invention, after performing the first-stage curing of the filling resin, the double-sided printed wiring board is a) between the copper foil with resin and the copper foil with resin. Laminate and press with heating. With this lamination press, for example, a hole-filled copper-clad laminate having four conductor layers can be produced. Specifically, the structure shown in FIG. 3A can be manufactured. In FIG. 3A, (16) is an insulating substrate, (17) is a conductor pattern, (18) is a thermo / thermosetting resin composition A or photo / thermosetting resin composition B, and (19) is with resin. The resin layer of copper foil, (20) is a copper foil of a copper foil with resin.

  In another aspect of the method for producing a hole-filled multilayer printed wiring board according to the present invention, after the first stage curing of the filling resin, the double-sided printed wiring board is a) between a copper foil with resin and a prepreg. Laminate and press. With this lamination press, for example, a hole-filled copper-clad laminate having three conductor layers can be produced. Specifically, the structure shown in FIG. 3B can be manufactured. 3B, (21) is an insulating substrate, (22) is a conductor pattern, (23) is a thermo / thermosetting resin composition A or light / thermosetting resin composition B, and (24) is with resin. The resin layer of copper foil, (25) is the copper foil of the copper foil with resin, and (26) is the prepreg.

  In the case of the above a) and b), when the double-sided printed wiring board is sandwiched between resin-coated copper foils, it is preferable to sandwich the copper foil so that it comes to the front side.

  Specifically, the lamination press can be performed with an open lamination apparatus, a vacuum lamination apparatus, or the like. Furthermore, these laminating apparatuses may be, for example, a hydraulic press, an autoclave press or the like. Furthermore, the vacuum hydraulic press may be a frame type, a box type, or the like.

  The lamination press is performed under heating. Heating is preferably performed so that the temperature is equal to or higher than the second-stage thermosetting temperature of the two-stage curable resin composition (in particular, the curing reaction start temperature of component [VI] or higher).

Specifically, as lamination press conditions, for example, 150 to 300 (particularly 180 to 230) ° C., 30 to 300 (particularly 60 to 240) minutes, pressure 10 to 100 (particularly 15 to 40) kgf / cm ² is preferable. .

  The following is performed by the lamination press. That is, the first-stage cured product of the filling resin is temporarily softened by heating during the laminating press, and the first-stage cured product protruding from the surface of the through hole is crushed and smoothed by the pressure of the press. The In such a smoothed state, the second-stage curing of the first-stage cured product is performed by heating at the time of the lamination press, and at the same time, the thermosetting in the B-stage state of the resin-coated copper foil or prepreg The resin is completely cured. In this manner, a hole-filled copper-clad laminate with a highly smooth surface is produced without polishing.

  In the method for manufacturing a hole-filled multilayer printed wiring board of the present invention, a conductor pattern is then formed from the copper foil on the surface layer of the hole-filled copper-clad laminate. The conductor pattern can be formed, for example, by a subtractive method or an additive method.

  In the case of the subtractive method, specifically, the conductor pattern may be formed as follows. That is, etching resist processing may be performed on the copper foil surface, etching may be performed, and then the etching resist may be removed.

  As the etching resist processing, for example, after coating a dry film, after exposing and curing through a pattern mask to form a resist, a dry film (laminate) method, after previously covering unnecessary portions of the conductor foil with an organic resist, Examples thereof include an electrodeposition resist method in which the conductor pattern portion is coated with a metal resist by electrodeposition and then only the organic resist is removed.

  Examples of the etchant include ferric chloride etchant, cupric chloride etchant, alkaline etchant, hydrogen peroxide / sulfuric acid, and the like. These may be appropriately selected according to the type of etching resist processing.

  The etching resist may be removed by, for example, spraying a resist stripping solution such as an aqueous sodium hydroxide solution from the spray nozzle or the like onto the panel surface to wash away the resist.

  As described above, the hole-filled multilayer printed wiring board of the present invention is manufactured. Specifically, the structures shown in FIGS. 3C and 3D can be manufactured. 3C, (27) is an insulating substrate, (28) and (31) are conductor patterns, (29) is a thermo / thermosetting resin composition A or light / thermosetting resin composition B, (30 ) Is a resin layer of resin-coated copper foil.

  3D, (32) is an insulating substrate, (33) and (36) are conductor patterns, (34) is a thermo / thermosetting resin composition A or light / thermosetting resin composition B, (35) is A resin layer (37) of a copper foil with resin is a prepreg.

  Although the present invention has been described above with respect to the hole-filled multilayer printed wiring board, those skilled in the art can easily modify and expand the present invention. For example, if a double-sided printed wiring board is sandwiched and pressed between the prepreg and the prepreg instead of a) the copper foil with resin and the copper foil with resin, or b) the copper foil with resin and the prepreg, A hole-filled printed wiring board (specifically, such as that shown in FIG. 3E) is manufactured.

  In FIG. 3E, (38) is an insulating substrate, (39) is a conductor pattern, (40) is a thermo / thermosetting resin composition A or light / thermosetting resin composition B, and (41) is a prepreg.

  Furthermore, the hole-filled multilayer printed wiring board shown in FIGS. 3C and 3D above, and the hole-filled printed wiring board shown in FIG. 3E are appropriately combined as an inner layer material or an outer layer material, if these are laminated and pressed, A desired hole-filled multilayer printed wiring board having a larger number of layers and a more complicated layer structure can be manufactured.

  Furthermore, a hole-filled multilayer printed wiring board having a desired number of layers can be manufactured by using an unhole-filled single-sided printed wiring board or an unhole-filled multilayer printed wiring board instead of the unhole-filled double-sided printed wiring board as a raw material.

  Furthermore, a hole-filled multilayer printed wiring board having a desired layer structure can be manufactured by using another adhesive sheet or other interlayer material instead of the resin-coated copper foil or prepreg.

Hereinafter, the present invention will be described more specifically with reference to the drawings.
<Preparation of thermosetting / thermosetting resin composition>
Preparation examples 1 to 3
A mixture of component [I] and component [II], component [III], component [V], component [VI], and other blending components were sequentially added and mixed with stirring. Subsequently, it was uniformly dispersed with a three-roll mill. The obtained uniform dispersion was vacuum degassed to prepare thermo-thermosetting resin compositions (Preparation Examples 1 to 3). Table 5 shows each blending component and blending amount (parts by weight).

<Preparation of light / thermosetting resin composition>
Preparation Example 4
Ingredient [I], ingredient [II], ingredient "IV", ingredient [V], ingredient [VI], and other compounding ingredients were added in order and mixed with stirring, and then uniformly dispersed in a three-roll mill. The obtained uniform dispersion was vacuum degassed to prepare a photo / thermosetting resin composition (Preparation Example 4) Table 5 shows each compounding component and compounding amount (parts by weight).

<Manufacture of a hole-filled multilayer printed wiring board filled with a thermo-thermosetting resin composition>
Example 1
As a double-sided printed wiring board, a conductor pattern layer [FIG. 1A, (2)] is provided on both sides of an insulating substrate [FIG. 1A, (1)], and the inner wall of the through hole [FIG. 1A, (3)] is copper-coated. [Copper circuit thickness is 40μ, L / S = 75μ] was used.

  On the double-sided printed wiring board, the thermo-thermosetting resin composition of Preparation Example 1 [FIG. 1B, (4)] was mask-printed with a 150-mesh stainless screen to fill and fill the through holes.

  Next, the hole-filled double-sided printed wiring board was heated to 150 ° C. in a heating furnace, and primary curing was performed at this temperature for 30 minutes. After the primary curing, the surface hardness of the primary thermoset was examined by the pencil hardness method (JISK-5400). The results are shown in Table 7.

  Next, a copper foil with resin was laminated on both surfaces of the double-sided printed wiring board to form a double-sided copper-clad laminate. In FIG. 1C, (5) is a resin layer of a copper foil with resin, and (6) is a copper foil of the copper foil with resin.

  Next, the double-sided copper-clad laminate was heated and vacuum-pressed according to the pressing conditions shown in Table 6, and the resin layer of the resin-coated copper foil and the secondary thermoset of the primary thermoset were simultaneously subjected to hole filling double-sided copper. A tension laminate was produced. [FIG. 1C].

  Next, conductor patterns [FIG. 1D, 7] were formed on both surfaces of the hole-filled double-sided copper-clad laminate as follows. First, using a dry film, an etching resist was formed by a dry film (laminate) method. That is, a dry film was laminated on both surfaces of a hole-filled double-sided copper-clad laminate, a negative film (pattern mask) was overlaid, and exposed and cured with an ultra-high pressure mercury lamp.

  Next, the carrier film of the dry film was peeled off, and a developer (1% sodium carbonate solution) was sprayed and developed on the exposed resist surface from a spray nozzle, and then washed with water to form a resist pattern.

Next, etching was performed. That is, a ferric chloride solution (36% by weight) was sprayed from both sides of the resist-coated double-sided copper-clad laminate from a spray nozzle to dissolve and remove unnecessary copper foil. After completion of the etching, a 3% aqueous sodium hydroxide solution was sprayed from a spray nozzle to wash away the etching resist while swelling.
As described above, a hole-filled multilayer printed wiring board (Example 1) of the present invention was produced [FIG. 1D].

Example 2
As the thermo-thermosetting resin composition that fills and fills the through hole, Preparation Example 2 is used instead of Preparation Example 1, and the heating temperature for primary curing is 120 ° C. instead of 150 ° C. A hole-filled multilayer printed wiring board (Example 2) was manufactured in the same manner as in Example 1 above.

Example 3
As a thermo / thermosetting resin composition that fills and fills the through hole, Preparation Example 3 is used instead of Preparation Example 1, and the heating temperature for primary curing is 110 ° C. instead of 150 ° C. A hole-filled multilayer printed wiring board (Example 3) was manufactured in the same manner as in Example 1 above.

Comparative example 1
As a double-sided printed wiring board, a conductor pattern layer provided on both sides of an insulating substrate and the inner wall of the through hole being copper-coated [copper circuit thickness is 40 μ, L / S = 75 μ] was used.

  On the double-sided printed wiring board, the thermosetting / thermosetting resin composition of Preparation Example 3 was mask-printed with a 150-mesh stainless screen to fill and fill in the recesses between the through holes and the conductor patterns.

  Next, the hole-filled double-sided printed wiring board was heated to 110 ° C. in a heating furnace, and primary curing was performed at this temperature for 30 minutes. After the primary curing, the surface hardness of the primary thermoset was examined by the pencil hardness method (JISK-5400). The results are shown in Table 7.

  Thereafter, the surface including the primary cured film was first polished 4 times with a 600th ceramic buff and then polished 4 times with an 800th nonwoven buff.

  Next, a copper foil with resin was laminated on both surfaces of the double-sided printed wiring board to form a double-sided copper-clad laminate.

  Next, the double-sided copper-clad laminate was heated and vacuum-pressed according to the pressing conditions shown in Table 6, and the resin layer of the resin-coated copper foil and the secondary thermoset of the primary thermoset were simultaneously subjected to hole filling double-sided copper. A tension laminate was produced.

  Next, conductor patterns were formed on both surfaces of the hole-filled double-sided copper-clad laminate as follows. First, using a dry film, an etching resist was formed by a dry film (laminate) method. That is, a dry film was laminated on both surfaces of a hole-filled double-sided copper-clad laminate, a negative film (pattern mask) was overlaid, and exposed and cured with an ultra-high pressure mercury lamp.

  Next, the carrier film of the dry film was peeled off, and a developer (1% sodium carbonate solution) was sprayed and developed on the exposed resist surface from a spray nozzle, followed by washing with water to form a resist pattern.

Next, etching was performed. That is, a ferric chloride solution (36% by weight) was sprayed from both sides of the resist-coated double-sided copper-clad laminate from a spray nozzle to dissolve and remove unnecessary copper foil. After completion of the etching, a 3% aqueous sodium hydroxide solution was sprayed from a spray nozzle to wash away the etching resist while swelling.
A hole-filled multilayer printed wiring board (Comparative Example 1) was manufactured as described above.

<Manufacture of hole-filled multilayer printed wiring board filled with light / thermosetting resin composition>
Example 4
As a double-sided printed wiring board, a conductor pattern layer [FIG. 1A, (2)] is provided on both sides of an insulating substrate [FIG. 1A, (1)], and the inner wall of the through hole [FIG. 1A, (3)] is copper-coated. [Copper circuit thickness is 40μ, L / S = 75μ] was used.

  On the double-sided printed wiring board, the photo / thermosetting resin composition of Preparation Example 4 [FIG. 1B, (4)] was mask-printed with a 150 mesh stainless screen to fill and fill the through holes. .

Next, the double-sided printed wiring board filled in the hole was photocured by irradiating with light at an exposure amount of 1500 mj / cm ² using a high-pressure mercury lamp, and then the surface hardness of the photocured product was determined by the pencil hardness method (JISK− 5400). The results are shown in Table 7.

  Next, a copper foil with resin was laminated on both surfaces of the double-sided printed wiring board to form a double-sided copper-clad laminate. In FIG. 1C, (5) is a resin layer of a copper foil with resin, and (6) is a copper foil of the copper foil with resin.

  Next, the double-sided copper-clad laminate was heated and vacuum-pressed according to the pressing conditions in Table 6, and the primary thermal curing of the resin layer of the resin-coated copper foil and the secondary thermal curing of the photocured product were simultaneously performed, and the hole-filled double-sided copper A tension laminate was produced [FIG. 1C].

  Next, conductor patterns [FIG. 1D, 7] were formed on both surfaces of the hole-filled double-sided copper-clad laminate as follows. First, using a dry film, an etching resist was formed by a dry film (laminate) method. That is, a dry film was laminated on both surfaces of a hole-filled double-sided copper-clad laminate, a negative film (pattern mask) was overlaid, and exposed and cured with an ultra-high pressure mercury lamp.

  Next, the carrier film of the dry film was peeled off, and a developer (1% sodium carbonate solution) was sprayed and developed on the exposed resist surface from a spray nozzle, and then washed with water to form a resist pattern.

  Next, etching was performed. That is, ferric chloride solution (36% by weight) was sprayed from both sides of the resist-coated double-sided copper-clad laminate from a spray nozzle to dissolve and remove unnecessary copper foil. After completion of the etching, a 3% aqueous sodium hydroxide solution was sprayed from a spray nozzle to wash away the etching resist while swelling.

  As described above, a hole-filled multilayer printed wiring board (Example 4) of the present invention was produced [FIG. 1D].

Comparative example 2
As a double-sided printed wiring board, a conductor pattern layer [FIGS. 2A, (10)] is provided on both sides of an insulating substrate [FIGS. 2A, (9)], and the inner walls of the through holes [FIGS. 2A, (11)] are copper-coated. [Copper circuit thickness is 40μ, L / S = 75μ] was used.

  On the double-sided printed wiring board, the photo / thermosetting resin composition of Preparation Example 4 [FIG. 2B, (12)] was mask-printed with a 150 mesh stainless screen to fill and fill the through holes. .

Next, the double-sided printed wiring board filled with holes was photocured by irradiating light at an exposure amount of 1500 mj / cm ² using a high-pressure mercury lamp, and then the surface hardness of the photocured product was determined by the pencil hardness method (JISK− 5400). The results are shown in Table 7.

  Next, the surface including the primary cured film was first polished 4 times with a 600th ceramic buff and then polished 4 times with an 800th nonwoven buff [FIG. 2C].

  Next, a copper foil with resin was laminated on both surfaces of the double-sided printed wiring board to form a double-sided copper-clad laminate. In FIG. 2D, (13) is a resin layer of a copper foil with resin, and (14) is a copper foil of the copper foil with resin.

  Next, the double-sided copper-clad laminate was heated and vacuum-pressed according to the pressing conditions in Table 6, and the primary thermal curing of the resin layer of the resin-coated copper foil and the secondary thermal curing of the photocured product were simultaneously performed, and the hole-filled double-sided copper A tension laminate was produced [FIG. 2D].

  Next, a conductor pattern [FIG. 2E, (15)] was formed on both surfaces of the hole-filled double-sided copper-clad laminate as follows. First, using a dry film, an etching resist was formed by a dry film (laminate) method. That is, a dry film was laminated on both surfaces of a hole-filled double-sided copper-clad laminate, a negative film (pattern mask) was overlaid, and exposed and cured with an ultra-high pressure mercury lamp.

  Next, the carrier film of the dry film was peeled off, and a developer (1% sodium carbonate solution) was sprayed and developed on the exposed resist surface from a spray nozzle, and then washed with water to form a resist pattern.

Next, etching was performed. That is, ferric chloride solution (36% by weight) was sprayed from both sides of the resist-coated double-sided copper-clad laminate from a spray nozzle to dissolve and remove unnecessary copper foil. After completion of the etching, a 3% aqueous sodium hydroxide solution was sprayed from a spray nozzle to wash away the etching resist while swelling.
A hole-filled multilayer printed wiring board (Comparative Example 2) was produced as described above [FIG. 2E].

<Properties of hole-embedded multilayer printed wiring board (Examples 1 to 4 and Comparative Examples 1 and 2)>
The flatness of the hole filling portion of the obtained hole filling multilayer printed wiring board was examined. That is, the flatness of the surface copper foil of the hole-filled multilayer printed wiring board was examined with a surface roughness meter. The results are shown in Table 7.

  The resulting hole-filled multilayer printed wiring board was examined for solder heat resistance and flatness after solder heat resistance as follows. That is, the hole-filled multilayer printed wiring board was immersed in molten solder at 260 ° C. for 60 seconds, and then the presence or absence of swelling / peeling and the flatness of the surface copper foil were examined. The results are shown in Table 7.

  The dimensional change of the obtained hole-filled multilayer printed wiring board was investigated. That is, the distance (about 480 mm) between the two guide pins in the long side direction of the substrate of the hole-filled multilayer printed wiring board was examined. The results are shown in Table 7.

  The cost for polishing the obtained hole-filled multilayer printed wiring board was examined. In other words, in addition to the presence of personnel costs, power costs, water costs, etc., the necessity of replacement due to consumption of buffs and belt sanders was examined. The results are shown in Table 7.

  As is apparent from Table 7 above, the hole-filled multilayer printed wiring boards (Examples 1 to 4) according to the present invention, which do not require polishing after primary curing, are not polished, so that the printed wiring board manufacturing process is performed. In addition, it is possible to reduce costs related to polishing such as labor costs, power costs, and water costs. Furthermore, deformation (dimensional change) of the substrate due to polishing can be avoided.

  Further, the flatness of the hole-filled portion, which is a concern due to not performing polishing, is not different from the hole-filled multilayer printed wiring board (Comparative Examples 1 and 2) that has been polished, and the hole-filled multilayer printed wiring according to the present invention. It can be said that a board (Examples 1-4) is excellent also in the flatness of a hole filling part. Further, the hole-filled multilayer printed wiring boards (Examples 1 to 4) according to the present invention have no problem even if the solder heat resistance and the flatness after the solder heat resistance are not polished. I understand.

  On the other hand, in the hole-filled multilayer printed wiring board (Comparative Examples 1 and 2) that has been polished after primary curing, the manufacturing process of the printed wiring board increases, and costs related to polishing such as labor costs, power costs, and water costs arise. . Further, deformation (dimensional change) of the substrate occurs due to polishing.

It is a manufacturing-process figure of the hole-filled multilayer printed wiring board which does not require grinding | polishing which concerns on this invention, and shows sectional drawing of a printed wiring board and a double-sided copper clad laminated board. It is a manufacturing-process figure of the hole-filled multilayer printed wiring board which performs grinding | polishing which concerns on a comparative example, and shows sectional drawing of a printed wiring board and a double-sided copper clad laminated board. Sectional drawing of the hole-filled copper foil laminated board and hole-filled (multilayer) printed wiring board which concern on this invention is shown.

Explanation of symbols

1, 9, 16, 21, 27, 32, 38: Insulating substrate.
2, 7, 10, 15, 17, 22, 28, 31, 33, 36, 39: conductor pattern.
3, 11: Through hole.
4, 12, 18, 23, 29, 34, 40: Thermo / thermosetting resin composition A or photo / thermosetting resin composition B.
5, 13, 19, 24, 30, 35, 41: Resin layer of copper foil with resin.
6, 14, 20, 25: Copper foil of resin-coated copper foil.
8: Concave part between conductor patterns.
26, 37: Pre-preg.

Claims (6)

Fill the through-hole of the double-sided printed wiring board with a two-stage curable resin composition, perform the first-stage curing of the filled resin by heating at 100 to 200 ° C. or UV irradiation, and a) double-sided printed wiring board Foil and copper foil with resin, or b) sandwiched between copper foil with resin and prepreg, after laminating and pressing at the second stage curing temperature or higher, and forming a conductor pattern from the copper foil of the surface layer To manufacture a hole-filled multilayer printed wiring board. The two-stage curable resin composition contains the following components [I], [II], [III], [V], and [VI], or a thermo / thermosetting resin composition A, or the following component [I] 2. The method for producing a hole-filled multilayer printed wiring board according to claim 1, which is a photo-thermosetting resin composition B containing [II], [IV], [V], and [VI]. .
[I]: Unsaturated fatty acid partial adduct of epoxy resin.
[II]: (Meth) acrylates.
[III]: radical thermal polymerization initiator.
[IV]: Photocrosslinking agent.
[V]: Epoxy resin.
[VI]: Latent curing agent.   Component [V]: The epoxy resin is a crystalline epoxy resin and / or a liquid epoxy resin, The manufacturing method of the hole-filling multilayer printed wiring board of Claim 2.   A hole-filled multilayer printed wiring board manufactured by the manufacturing method according to claim 1. The two-stage curable resin composition contains the following components [I], [II], [III], [V], and [VI], or a thermo / thermosetting resin composition A, or the following component [I] , [II], [IV], [V], and [VI], a photo / thermosetting resin composition B,
And the two-stage curable resin composition used for the manufacturing method of the hole-filling multilayer printed wiring board of Claim 1.
[I]: Unsaturated fatty acid partial adduct of epoxy resin.
[II]: (Meth) acrylates.
[III]: radical thermal polymerization initiator.
[IV]: Photocrosslinking agent.
[V]: Epoxy resin.
[VI]: Latent curing agent.   The two-stage curable resin composition according to claim 5, wherein the component [V]: the epoxy resin is a crystalline epoxy resin and / or a liquid epoxy resin.

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